铁纳米氧化物应用于选择性催化氢化及氢转移反应的研究

The main purpose of this research is to apply iron oxide nanoparticles in catalytic selective (transfer) hydrogenation. Our proposal aims to develop highly efficient and highly selective hydrogen transfer catalysts, and discover the effect mechanism of iron oxide in the catalytic reactions. The following selective hydrogenation reaction will be included in this study: selective reduction of nitrostyrene, selective reduction of unsaturated carbonyl compounds, selective hydrogenation of nitro aldehyde, reductive amination and cyano reduction to primary amines. The iron oxide nanoparticles will be applied as active site, promoter and magnetic carrier. The active iron oxide that are combined with 2D, 3D nano supporters or magnetic carrier will be developed as green and inexpensive catalyst for transfer hydrogenation. Less amount but high dispersed noble metal clusters and sub nanometer particles will be loaded into the iron oxide (Fe3O4, Fe2O3 and FeOOH) with tunable nanostructures and diverse morphologies in order to develop more active and less expensive catalyst. Meanwhile, the reaction mechanism of iron oxide nanoparticles in the catalytic transfer hydrogenation will be explored. The generation, storage and transformation process of the active hydrogen species on iron oxide will be explored, and the adsorption and conversion of organic functional groups on catalysts will be also investigated. We will study the kinetics of hydrogen transfer reaction, and try to illustrate the scientific nature of catalytic process. The combined discussion of this research will be the improvement of the selective transfer hydrogenation theory.

本课题旨在拓展铁纳米氧化物在催化选择性氢转移反应中的应用，开发高效、高选择性的氢转移催化剂，并研究氧化铁在其中的作用机制。本课题以几种选择性氢化反应为模型，包括硝基烯烃的还原、不饱和羰基化合物的选择性加氢、硝基醛的选择性还原、还原胺化反应以及氰基还原制伯胺等，探讨铁纳米氧化物分别作为活性组分、助催化剂以及磁性载体的作用。利用活性纳米氧化铁，结合2D、3D纳米载体以及磁性载体的使用，发展新型廉价、环保的氢转移催化剂；使用低载量、高分散的贵金属原子团簇或亚纳米颗粒作为活性组分，与Fe3O4、Fe2O3、FeOOH等各种组成、结构、形貌可调变的铁氧化物的相结合，构造高效、高选择性的氢转移催化剂，同时探索铁纳米氧化物的作用机制，通过研究纳米氧化铁上活性氢组分的产生、存储及转化过程，以及有机官能团在催化剂上的吸附及转变，并结合反应的动力学研究，揭示催化过程的科学本质，发展选择性氢转移理论。

摘要：项目《铁纳米氧化物应用于选择性催化氢化及氢转移反应的研究》主要完成了以下几项工作：（1）以铁基纳米氧化物作为活性组分，研究了催化氢转移硝基还原反应；（2）综合讨论了催化氢转移反应过程中的选择性机理；（3）铁氧化物载体在催化氢化及氢转移反应的研究；（4）选择性氢转移反应选择性还原腈制备伯胺和仲胺的反应及机制。此外，在研究过程中发现，铁系元素在催化碳载体生长、催化氧化钨-碳化钨的转化等方面都发挥了重要作用，生成的产物在电催化及储能方向有优良的性质。研究结果共发表了SCI论文26篇，在研期间获批相关专利3项，培养博研究生4人，硕士研究生12人，本科毕业论文21人。